Journal article
Synthesis, characterization and structural comparisons of phosphonium and arsenic dithiocarbamates with alkyl and phenyl substituents
Polyhedron, Vol.75, pp.110-117
06/17/2014
DOI: 10.1016/j.poly.2014.03.003
Abstract
The synthesis and characterization of the new arsenic dithiocarbamate complex As[S2CNPh2]3 and three new tetraphenylphosphonium dithiocarbamates are reported, along with the structures of [PPh4][S2CNEt2], [PPh4][S2CN(CH2)5], As[S2CN(CH2)5]3, As[S2CNPh2]3, and As[S2CN(CH2)5]2I. Comparison of the As[S2CNR2]3 complexes (R=alkyl versus phenyl) reveal similar bond distances, but differences in the C–S stretching frequencies. [Display omitted] The synthesis and characterization of the new arsenic dithiocarbamate complex As[S2CNPh2]3 and three new phosphonium dithiocarbamates [PPh4][S2CNR2], where R2=Et2, (CH2)5 and Ph2, are reported. As[S2CNPh2]3 was prepared by treating AsI3 with three equivalents of NaS2CNPh2 in a 2:1 mixture of H2O and EtOH. The precipitate that formed was recrystallized from hot toluene to yield yellow prisms of As[S2CNPh2]3 suitable for single-crystal X-ray diffraction (XRD). Attempts to prepare the known compound As[S2CN(CH2)5]3 using a similar route resulted in a mixture of As[S2CN(CH2)5]3 and the mixed iodide species As[S2CN(CH2)5]2I. Single-crystals of both compounds were isolated from concentrated Et2O/CHCl3 solutions and their structures are described here for the first time. [PPh4][S2CNR2] salts were prepared for comparison to arsenic dithiocarbamates by metathesis reactions with PPh4Br and NaS2CNR2 in acetonitrile. All three salts could be obtained in high-purity from MeCN/Et2O solutions and crystal structures of [PPh4][S2CNEt2] and [PPh4][S2CN(CH2)5] reveal charge-separated phosphonium cations and dithiocarbamate anions. The five new crystal structures are used to compare dithiocarbamate bond distances and angles in the presence and absence of arsenic. Nuclear magnetic resonance (NMR) spectra, infrared (IR) spectra, microanalyses, and melting points of the compounds are reported.
Details
- Title: Subtitle
- Synthesis, characterization and structural comparisons of phosphonium and arsenic dithiocarbamates with alkyl and phenyl substituents
- Creators
- Courtney M Donahue - The George Washington University, Department of Chemistry, 725 21st St., NW Washington, DC 20052, USAIsabella K Black - The George Washington University, Department of Chemistry, 725 21st St., NW Washington, DC 20052, USASamantha L Pecnik - The George Washington University, Department of Chemistry, 725 21st St., NW Washington, DC 20052, USAThomas R Savage - The George Washington University, Department of Chemistry, 725 21st St., NW Washington, DC 20052, USABrian L Scott - Los Alamos National Laboratory, Los Alamos, NM 87545, USAScott R Daly - The George Washington University, Department of Chemistry, 725 21st St., NW Washington, DC 20052, USA
- Resource Type
- Journal article
- Publication Details
- Polyhedron, Vol.75, pp.110-117
- Publisher
- Elsevier Ltd
- DOI
- 10.1016/j.poly.2014.03.003
- ISSN
- 0277-5387
- Grant note
- DOI: 10.13039/100007108, name: George Washington University
- Language
- English
- Date published
- 06/17/2014
- Academic Unit
- Chemistry
- Record Identifier
- 9983985957502771
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